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1 2004

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Efekty powierzchniowej struktury metali w procesach elektrochemicznych

Sobkowski J., Jurkiewicz-Herbich M.

Wiadomości Chemiczne

2004

[Z] 58, 5-6

449--476

It is known that both the nature and structure of a metal have a great influence on electrochemical processes. Interpretation of a mechanism of electrochemical reactions that occur on polycrystalline electrodes is often complicated because of their heterogeneous structure consisting of randomly distributed monocrystals on the surface. To avoid this problem, electrodes with well defined surfaces are commonly used in electrochemical experiments. In this paper, effects of the surface structure of a metallic electrode on properties of the double layer of the metal/solution interface, electrosorption and also on the electrochemical reactions has been reviewed. The presented data refer mainly to the basic planes of monocrystalline electrodes of face-centered cubic system. In first three chapters problems of the double layer structure of monocrystalline electrodes, the correlation of the potential of zero charge and work function, and the competition of a substrate and water molecules in the electrosorption process in relation to the hydrophilicity of metals are discussed. In chapters 4 and 5 the influence of the surface structure on the adsorption of organic molecules, strongly and weakly interacting with the electrode surface, is reviewed. It was shown that the surface concentration of adsorbate depends not only on the number of adsorption sites (assumed as the surface atom density) but also on the geometry of adsorbed molecule as well as on the kind and size of the supporting electrolyte anions. The latter play a very important role when the interaction of an adsorbed molecule and a metal is weak. Chapter 6 concerns the role of the electrode surface structure in the hydrogen ion discharge and also underpotential deposition of ions. The relationship between electrocatalytic properties of an electrode and its surface structure is presented in chapter 7. The kinetics of oxidation of methanol and formic acid at different planes of the platinum electrode and various products of the reduction of carbon oxide on copper monocrystalline electrodes are given as examples.